Alkyl Transfer Reactivity in the First Octahedral Isocyanide Complex of

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Organometallics 2004, 23, 2568-2572

Alkyl Transfer Reactivity in the First Octahedral Isocyanide Complex of Nickel(II) Enmanuel Boı´llos and Daniel Miguel* Departamento de Quı´mica Inorga´ nica, Facultad de Ciencias, Universidad de Valladolid, E-47005 Valladolid, Spain Received December 1, 2003

[Ni{S2P(OEt)2}2] (1) reacts with 2 equiv of CNXyl (Xyl ) 2,6-dimethylphenyl) to afford [Ni{S2P(OEt)2}2(CNXyl)2] (2), which, as confirmed by X-ray crystallography, is the first octahedral isocyanide complex of Ni(II). Reaction of 2 with PCy3 (2 equiv) produces squareplanar [Ni{S2P(O)(OEt)}(PCy3)(CNXyl)] (3). When 2 is reacted with only 1 equiv of PCy3, the final product is the square-planar complex [Ni{S2P(O)(OEt)}(CNXyl)2] (4), containing two isocyanide ligands. Compound 4 reacts with 2-fold excess PCy3 to give 3 via isocyanide displacement. Both 3 and 4 contain one ethyldithiophosphate ligand, which is produced by the transfer of one ethyl group from a coordinated diethyl dithiophosphate of complex 2 to the leaving diethyl dithiophosphate ligand. Experimental evidence indicates that the phosphine plays a significant role in the alkyl transfer. Moreover, reaction of 1 with 2 equiv of N-p-tolyl-2-iminopyridine affords octahedral [Ni{S2P(OEt)2}{2-pyCHdNC6H4-Me-4}2][S2P(OEt)2] (5), in which both free and coordinated diethyl dithiophosphate coexist without any transfer of alkyl. Introduction The chemistry of nickel(II) isocyanide complexes is dominated by the square-planar geometry. Only a few examples of pentacoordinate Ni(II) complexes containing isocyanides have been reported, and most of them are di- or polymetallic compounds where the pentacoordination is attained by the formation of a direct metal-metal bond.1 No report of structural characterization of a simple octahedral Ni(II) isocyanide complex can be found in the Cambridge Structural Database and, as far as we know, there has been no report on the preparation of such complexes. This is remarkable, since this class of complexes has attracted some interest in several fields, such as the activation of CO2,2 the polymerization of isocyanide catalyzed by Ni(II),3 and, more recently, the preparation of N-aryl Ni(II) carbenes from Ni(0) isocyanide complexes.4 Additionally, it is well-known that bis(1,1-dithiolato)nickel(II) complexes are able to add ligands to afford penta- or hexacoordinate complexes, although most of these reactions have * To whom correspondence should be addressed. Tel: int + 34 983 184096. Fax: int + 34 983 423013. E-mail: [email protected]. (1) Kubiak, C. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, U.K., 1995; Vol. 9, Chapter 1. (2) DeLaet, D. L.; del Rosario, R.; Fanwick, P. E.; Kubiak, C. P. J. Am. Chem. Soc. 1987, 109, 754. DeLaet, D. L.; Fanwick, P. E.; Kubiak, C. P. J. Chem. Soc., Chem. Commun. 1987, 1412. Lemke, F. R., DeLaet, D. L.; Gao, J.; Kubiak, C. P. J. Am. Chem. Soc. 1988, 110, 6904. (3) Deming, T. J.; Novak, B. M. J. Am. Chem. Soc. 1992, 114, 4400, 7296; 1993, 115, 9101. Visser, H. G. J.; Nolte, R. J. M.; Zwikker, J. W.; Drenth, W. J. Org. Chem. 1985, 50, 3133, 3138. Amabilino, D. B.; Ramos, E.; Serrano, J. L.; Veciana, J. Adv. Mater. 1998, 10, 1001. Amabilino, D. B.; Ramos, E.; Serrano, J. L.; Sierra, T.; Veciana, J. J. Am. Chem. Soc. 1998, 120, 9126. (4) Hou, H.; Gantzel, P. K.; Kubiak, C. P. J. Am. Chem. Soc. 2003, 125, 9564. Hou, H.; Gantzel, P. K.; Kubiak, C. P. Organometallics 2003, 22, 2817.

been done using N- or P-donor ligands.5 We wish to report here the preparation of the first octahedral isocyanide complex of nickel(II) and its reactivity with phosphines, which involves a change in the coordination number from 6 to 4, and simultaneous activation of a O-C(alkyl) bond of the dithiophosphate ester. Results and Discussion Addition of 2 mol equiv of CNXyl (Xyl ) 2,6-C6H6Me2) to a dichloromethane solution of [Ni{S2P(OEt)2}2] (1)6 causes an immediate color change from purple to red, and the IR monitoring indicates the coordination of the isocyanide (ν(CN) 2181 cm-1 vs 2123 cm-1 for the free ligand).7 The resulting complex 2 (Scheme 1) was isolated and characterized by analytical and spectroscopic methods. The octahedral environment around Ni was confirmed by X-ray crystallography (Tables 1 and 2). The molecule (Figure 1) is centrosymmetric, and the two isocyanide ligands are trans to each other, which is consistent with the appearance of only one ν(CN) band in the IR spectrum. The coordination of the isocyanide (5) Sacconi, L.; Mani, F.; Bencini, A. In Comprehensive Coordination Chemistry; Wilkinson, G., Guillard, R. D., McCleverty, J. A., Eds.; Pergamon Press: Oxford, U.K., 1987; Vol. 5, Chapter 50. (6) Coldbery, D. E.; Fernelius, W. C.; Shamma, M. Inorg. Synth. 1960, 6, 142. (7) One reviewer asked for an explanation: when isocyanides are coordinated to a monopositive or dipositive metal ion such as Cr(0) or Ni(0), little or no back-donation occurs, and the CN stretching band is shifted to a higher frequency as a result of the inductive effect of the metal. When isocyanides are coordinated to zero-valent metals, backdonation is extensive and the CN stretching band is shifted to lower frequency. See: Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds, 5th ed.; Wiley: New York, 1997; Part B (Applications in Coordination, Organometallic, and Bioinorganic Chemistry), p 115. Cotton, F. A.; Zingales, F. J. Am. Chem. Soc. 1961, 83, 351.

10.1021/om0343364 CCC: $27.50 © 2004 American Chemical Society Publication on Web 04/14/2004

The First Octahedral Isocyanide Complex of Ni(II)

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Table 1. Crystal Data and Refinement Details for [Ni{S2P(OEt)2}2(CNXyl)2] (2), [Ni{S2P(O)(OEt)}(CNXyl)(PCy3)] (3), [Ni{S2P(O)(OEt)}(CNXyl)2] (4), and [Ni{S2P(OEt)2}{2-pyCHdNC6H4-Me-4}2][S2P(OEt)2] (5) formula fw cryst syst space group a, Å b, Å c, Å R, deg β, deg γ, deg V, Å3 Z T, K Fcalcd, g cm-3 F(000) λ(Mo KR), Å cryst size, mm; color µ, mm-1 scan range, deg abs cor corrn factors (min, max) no. of rflns measd no of indep rflns no of rflns with I e 2σ(I) GOF on F2 no. of params residuals R1, wR2

2

3

4

5

C26H38N2NiO4P2S4 691.47 triclinic P1 h (No. 2) 10.911(3) 10.932(3) 14.640(4) 101.227(4) 90.509(5) 96.954(4) 1699.1(8) 2 293 1.352 724 0.710 73 0.28 × 0.18 × 0.12; pale green 0.943 1.42 e θ e 23.5 SADABS 1.0000, 0.8020 10 582 4825 4020 1.007 363 0.0595, 0.1907

C29H47NNiO2P2S2‚CH2Cl2 711.37 monoclinic P21/c (No. 14) 16.522(1) 13.903(1) 15.309(1) 90 90.104(2) 90 3516.5(4) 4 293 1.344 1504 0.710 73 0.22 × 0.21 × 0.17; yellow 0.941 1.23 e θ e 23.29 SADABS 1.000, 0.8673 15 501 5065 4096 1.026 364 0.0398, 0.1228

C20H23N2NiO2PS4 477.20 monoclinic C2/c (No. 15) 15.406(5) 13.201(4) 22.338(7) 90 102.738(6) 90 4431(2) 8 293 1.431 1984 0.710 73 0.14 × 0.08 × 0.06; orange 1.154 1.87 e θ e 23.28 SADABS 1.000, 0.4403 9703 3186 1683 1.003 258 0.0514, 0.0812

C34H44N4NiO4P2S4 821.62 triclinic P1 h (No. 2) 11.657(6) 13.101(7) 15.337(8) 98.199(9) 109.12(1) 110.843(9) 1977(2) 2 293 1.380 860 0.710 73 0.23 × 0.14 × 0.08; orange 0.824 1.47 e θ e 23.32 SADABS 1.000, 0.6629 8722 5541 3476 1.003 449 0.0563, 0.1348

Scheme 1

ligands in 2 is weaker than in the square-planar complexes (cf. Ni-C distances and ν(CN) bands for 2 with those of 3 and 4 below). In the equatorial plane, the Ni atom and the two dithiolato ligands are arranged in a fashion very close to that found in the structural determination8 of the square-planar starting compound 1. Upon addition of 2 equiv of phosphine, complex 2 slowly undergoes transformation into the new species 3, in which one phosphine is incorporated into the coordination sphere of Ni, replacing one dithio ligand and one isocyanide, thus affording a four-coordinate square-planar complex. This has been confirmed by X-ray crystallography for 3 (Figure 2 and Table 3).The structure determination revealed also that one ethyl group of the remaining coordinated dithio ligand had (8) Fernando, Q.; Green, C. D. J. Inorg. Nucl. Chem. 1967, 29, 647.

been lost to give O-ethyl dithiophosphate. As outlined in Scheme 1, complex 3 can also be obtained by reacting 1 successively with 1 equiv of PCy3 and 1 equiv of isocyanide (see Experimental Section). Surprisingly, when the octahedral bis(isocyanide) complex 2 was reacted with only 1 equiv of phosphine, the resulting compound retained the two isocyanide ligands, and the phosphine was not incorporated, thus affording compound 4. Although the phosphine was absent from the final product, its presence in the reaction mixture seems to be necessary, since complex 2 does not transform into 4 even in the presence of excess isocyanide. Compound 4 undergoes replacement of isocyanide by phosphine, and the complete transformation from 4 to 3 can be achieved by using a 2-fold excess of PCy3. In contrast, complex 3 does not react even in the presence of excess isocyanide in refluxing toluene for several hours. As was the case with compound 3, an X-ray determination (Figure 3 and Table 4) confirmed that in 4 the Ni atom lies in a square-planar four-coordinate environment, and again one ethyl group of the dithiophosphate ligand has been lost. There are only a few precedents for this O-C activation in Ni(II)9 and Mo(V)10 complexes, and its relevance in several fields has been recently emphasized, especially in connection with the enzymatic alkyl transfer from and to phosphate esters.10,11 It has been generally proposed that the alkyl group is transferred to the leaving dithiophosphate group to afford neutral O,O′,Striethyl dithiophosphate: EtSP(dS)(OEt)2. (9) Gastaldi, L.; Porta, P.; Tomlison, A. A. G. J. Chem. Soc., Dalton Trans. 1974, 1424. (10) Koffi-Sokpa, E. I.; Calfee, D. T.; Allred, B. R. T.; Davis, J. L.; Haub, E. K.; Rich, A. K.; Porter, R. A.; Mashuta, M. S.; Richardson, J. F.; Noble, M. E. Inorg. Chem. 1999, 38, 802. (11) Wilker, J. J.; Lippard, S. J. Inorg. Chem. 1997, 36, 969.

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Table 2. Selected Interatomic Distances (Å) and Angles (deg) in [Ni{S2P(OEt)2}2(CNXyl)2] (2)a Ni(1)-C(1)#1 Ni(1)-S(2)#1 Ni(1)-S(1) S(2)-P(1) P(1)-O(2) C(1)-N(1) Ni(51)-C(51) Ni(51)-S(51) Ni(51)-S(52) S(51)-P(51) P(51)-O(52) C(51)-N(51) C(1)#1-Ni(1)-C(1) C(1)-Ni(1)-S(2)#1 C(1)-Ni(1)-S(2) C(1)#1-Ni(1)-S(1) S(2)#1-Ni(1)-S(1) C(1)#1-Ni(1)-S(1)#1 S(2)#1-Ni(1)-S(1)#1 S(1)-Ni(1)-S(1)#1 S(52)-Ni(51)-S(52)#2 C(51)-Ni(51)-S(51) C(51)-Ni(51)-S(51)#2 S(51)-Ni(51)-S(51)#2 C(51)#2-Ni(51)-S(52) S(51)#2-Ni(51)-S(52) N(51)-C(51)-Ni(51) a

2.006(7) 2.5185(19) 2.5564(19) 1.986(3) 1.585(5) 1.164(8) 2.020(6) 2.5221(18) 2.5324(19) 1.982(3) 1.602(6) 1.151(8) 180.0(3) 88.23(18) 91.77(18) 89.27(17) 98.75(6) 90.73(17) 81.25(6) 180.000(1) 180.0 88.99(17) 91.01(17) 180.0 89.32(18) 98.19(6) 177.4(5)

Ni(1)-C(1) Ni(1)-S(2) Ni(1)-S(1)#1 S(1)-P(1) P(1)-O(1) N(1)-C(2) Ni(51)-C(51)#2 Ni(51)-S(51)#2 Ni(51)-S(52)#2 S(52)-P(51) P(51)-O(51) N(51)-C(52)

2.006(7) 2.5185(19) 2.5564(19) 1.979(2) 1.612(5) 1.403(8) 2.020(6) 2.5221(18) 2.5324(19) 1.985(3) 1.607(6) 1.419(8)

C(1)#1-Ni(1)-S(2)#1 C(1)#1-Ni(1)-S(2) S(2)#1-Ni(1)-S(2) C(1)-Ni(1)-S(1) S(2)-Ni(1)-S(1) C(1)-Ni(1)-S(1)#1 S(2)-Ni(1)-S(1)#1 C(1)-N(1)-C(2) C(51)-Ni(51)-C(51)#2 C(51)#2-Ni(51)-S(51) C(51)#2-Ni(51)-S(51)#2 C(51)-Ni(51)-S(52) S(51)-Ni(51)-S(52) C(51)-Ni(51)-S(52)#2 S(51)-Ni(51)-S(52)#2

91.77(18) 88.23(18) 180.0 90.73(17) 81.25(6) 89.27(17) 98.75(6) 176.5(6) 180.00(15) 91.01(17) 88.99(17) 90.68(18) 81.81(6) 89.32(18) 98.19(6)

Symmetry transformations: (#1) -x, -y, -z + 1; (#2) -x + 1, -y + 1, -z + 2.

Table 3. Selected Interatomic Distances (Å) and Angles (deg) in [Ni{S2P(O)(OEt)}(CNXyl)(PCy3)] (3) Ni(1)-C(1) Ni(1)-P(1) S(1)-P(2) P(1)-C(31) P(1)-C(21) P(2)-O(2)

Figure 1. Perspective view of one of the two crystallographically independent but chemically equivalent molecules of [Ni{S2P(OEt)2}2(CNXyl)2] (2), showing the atom numbering. The numbering of the second molecule can be obtained by adding 50 to the number in the label.

C(1)-Ni(1)-S(1) S(1)-Ni(1)-P(1) S(1)-Ni(1)-S(2) P(2)-S(1)-Ni(1) C(31)-P(1)-C(41) C(41)-P(1)-C(21) C(41)-P(1)-Ni(1) O(1)-P(2)-O(2) O(2)-P(2)-S(2) O(2)-P(2)-S(1) C(1)-N(1)-C(2)

1.820(4) 2.2166(9) 2.0371(12) 1.846(3) 1.851(3) 1.588(3) 173.40(11) 91.00(3) 87.15(4) 88.64(4) 105.11(14) 103.66(14) 109.74(11) 106.56(15) 108.94(12) 108.84(12) 176.0(4)

Ni(1)-S(1) Ni(1)-S(2) S(2)-P(2) P(1)-C(41) P(2)-O(1) N(1)-C(1) C(1)-Ni(1)-P(1) C(1)-Ni(1)-S(2) P(1)-Ni(1)-S(2) P(2)-S(2)-Ni(1) C(31)-P(1)-C(21) C(31)-P(1)-Ni(1) C(21)-P(1)-Ni(1) O(1)-P(2)-S(2) O(1)-P(2)-S(1) S(2)-P(2)-S(1) S(2)-P(2)-S(1)

2.1855(9) 2.2248(10) 2.0357(13) 1.846(3) 1.460(2) 1.151(4) 95.59(10) 86.25(11) 176.36(4) 87.60(4) 110.91(16) 112.05(11) 114.59(11) 118.87(12) 116.55(12) 96.56(5) 96.56(5)

necessarily to the transference of alkyl. Thus, the bis(dithiophosphate) complex 1 reacts with 2 equiv of N-ptolyl-2-iminopyridine, as depicted in Scheme 2, to afford the salt 5, via displacement of the O,O′ dithiophosphate anion. An X-ray determination reveals that 5 contains both coordinated and free dithiophosphate, without any transfer of alkyl (Figure 4 and Table 5).

Figure 2. Perspective view of the molecule of [Ni{S2P(O)(OEt)}(CNXyl)(PCy3)] (3), showing the atom numbering.

However, there are several experimental facts which suggests a more complex mechanism. In the first place, the presence of a leaving dithiophosphate does not lead

Figure 3. Perspective view of the molecule of [Ni{S2P(O)(OEt)}(CNXyl)2] (4), showing the atom numbering.

The First Octahedral Isocyanide Complex of Ni(II)

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Table 4. Selected Interatomic Distances (Å) and Angles (deg) in [Ni{S2P(O)(OEt)}(CNXyl)2] (4) Ni(1)-C(1) Ni(1)-S(1) S(1)-P(1) P(1)-O(1) N(1)-C(1) N(2)-C(2)

1.821(7) 2.1887(17) 2.023(2) 1.451(4) 1.148(7) 1.149(6)

C(1)-Ni(1)-C(2) C(2)-Ni(1)-S(1) C(2)-Ni(1)-S(2) P(1)-S(1)-Ni(1) O(1)-P(1)-O(2) O(2)-P(1)-S(1) O(2)-P(1)-S(2) C(1)-N(1)-C(11) C(3)-O(2)-P(1) N(2)-C(2)-Ni(1)

96.4(2) 175.5(2) 88.39(18) 87.72(8) 106.0(3) 108.64(19) 109.68(19) 177.9(6) 122.8(4) 176.7(6)

Ni(1)-C(2) Ni(1)-S(2) S(2)-P(1) P(1)-O(2) N(1)-C(11) N(2)-C(21) C(1)-Ni(1)-S(1) C(1)-Ni(1)-S(2) S(1)-Ni(1)-S(2) P(1)-S(2)-Ni(1) O(1)-P(1)-S(1) O(1)-P(1)-S(2) S(1)-P(1)-S(2) C(2)-N(2)-C(21) N(1)-C(1)-Ni(1) O(2)-C(3)-C(4)

1.831(6) 2.1894(19) 2.032(2) 1.585(5) 1.399(7) 1.393(7) 87.96(18) 171.2(2) 87.45(7) 87.47(8) 118.1(2) 117.5(2) 96.53(9) 177.0(6) 174.2(6) 110.2(7)

Scheme 2

In an early related precedent, the structure of [Ni{S2P(OMe)2}2(phen-Me2)] contains both monodentate and bidentate dithiophosphate, again without any alkyl transfer between them.12 Interestingly, the octahedral bis(isocyanide) complex 2 does not react with an excess of diimine, even in refluxing THF for several hours. The experimental results known so far indicate that the transfer of alkyl occurs only when phosphine is present in the reaction mixture, even in the case (formation of 4) when the phosphine is not incorporated into the final product. Additionally, IR monitoring of the reaction mixtures of 1 and 2 with PCy3/isocyanide reveals the formation, in the initial steps, of the complex [Ni(CNXyl)4], as deduced from the ν(CN) bands at 2030 and 2000 cm-1, identical with those of an authentic sample prepared as described in the literature.13 The Ni(0) complex slowly transforms into the final products 3 and 4, depending on the amount of phosphine available. This implies that some reduction and oxidation processes are involved in the mechanism. On the other hand, the monitoring of the crude reaction mixtures by 31P{1H]} NMR shows the presence of EtSP(dS)(OEt)2 (at δ 96.1 ppm), together with small amounts of phosphine sulfide and phosphine oxide, and no trace of the signal of [PCy3Et]+, suggesting that the phosphine activates the process through coordination to the metal atom in an intermediate, rather than being involved directly in the alkyl transfer. Some work is now in progress attempting to obtain conclusive information about the mechanism of this interesting C-O activation. Experimental Section All reactions were carried out in dry solvents under a nitrogen atmosphere. Details of the instrumentation and (12) Tomlison, A. A. G.; Furlani, C. J. Chem. Soc., Dalton Trans. 1974, 1420. (13) Kim, W. Y.; Chang, J. S.; Park, S. E.; Kubiak, C. P. Res. Chem. Intermed. 1999, 25, 459.

Figure 4. Perspective view of the molecule of [Ni{S2P(OEt)2}{2-pyCHdNC6H4-Me-4}2][S2P(OEt)2] (5), showing the atom numbering. Table 5. Selected Interatomic Distances (Å) and Angles (deg) in [Ni{S2P(OEt)2}{2-pyCHdNC6H4-Me-4}2][S2P(OEt)2] (5) Ni(1)-N(1) Ni(1)-N(2) Ni(1)-S(2) S(1)-P(1) P(1)-O(1) N(1)-C(11) N(2)-C(16) N(3)-C(31) N(4)-C(36) N(1)-Ni(1)-N(4) N(4)-Ni(1)-N(2) N(4)-Ni(1)-N(3) N(1)-Ni(1)-S(2) N(2)-Ni(1)-S(2) N(1)-Ni(1)-S(1) N(2)-Ni(1)-S(1) S(2)-Ni(1)-S(1)

2.084(5) 2.095(4) 2.4403(19) 1.933(3) 1.5057 1.322(7) 1.282(7) 1.331(7) 1.257(7)

Ni(1)-N(4) Ni(1)-N(3) Ni(1)-S(1) S(2)-P(1) P(1)-O(2) N(1)-C(15) N(2)-C(17) N(3)-C(35) N(4)-C(37)

2.090(4) 2.110(5) 2.468(2) 1.968(3) 1.527(6) 1.353(7) 1.432(7) 1.343(7) 1.429(7)

89.92(18) 90.57(16) 78.36(19) 93.08(13) 94.16(12) 99.56(14) 175.90(13) 82.55(6)

N(1)-Ni(1)-N(2) N(1)-Ni(1)-N(3) N(2)-Ni(1)-N(3) N(4)-Ni(1)-S(2) N(3)-Ni(1)-S(2) N(4)-Ni(1)-S(1) N(3)-Ni(1)-S(1) N(3)-Ni(1)-S(1)

78.11(18) 164.03(17) 91.06(18) 174.83(14) 99.46(14) 92.80(13) 91.89(13) 91.89(13)

experimental procedures have been given elsewhere.14 Literature procedures for the preparation of starting materials are quoted in each case. Ligands and other reagents were purchased and used without purification, unless otherwise stated. [Ni{S2P(OEt)2}(CNXyl)2] (2). To a solution of 1 (0.214 g, 0.5 mmol)6 in CH2Cl2 (20 mL) was added 2,6-dimethylphenyl isocyanide (CNXyl; 0.131 g, 1 mmol), and the mixture was stirred for 0.5 h at room temperature. The color changed from purple to deep red. The solvent was evaporated, and the residue was washed several times with hexane. The solid was dissolved in the minimum amount of CH2Cl2 and layered with hexane. Slow diffusion at -20 °C afforded compound 2 as green crystals. Yield: 0.048 g, 69%. Anal. Calcd for C26H38N2NiO4P2S4: C, 45.16; H, 5.54; N, 4.05. Found: C, 44.93; H, 5.28; N, 4.09. IR (CH2Cl2): ν(CN) 2181 cm-1. 1H NMR (Me2CO-d6; δ (ppm)): 8.12 (t(7), 2H, H4 of Xyl), 6.71 (d(7), 4H, H3and H5of Xyl), 4.37 (m (br), 8H, POCH2), 1.72 (m (br), 12H, POCH2CH3), 1.44 (s, 12H, CH3 of Xyl). 31P{1H} NMR (δ (ppm)): 78 (v br). [Ni{S2P(O)(OEt)}(CNXyl)(PCy3)] (3). (a) From 1. To a purple solution of 1 (0.214 g, 0.5 mmol)6 in CH2Cl2 (20 mL) was added PCy3 (0.28 g, 1 mmol), and the solution turned green. After the solution was stirred for 1 h, CNXyl (0.065 g, 0.5 mmol) was added and the solution turned red immediately. The mixture was stirred for 5 h, and then the solvent was evaporated in vacuo. The residue was washed with Et2O to extract a small amount of starting 1. The resulting solid was redissolved in CH2Cl2 and filtered. Addition of hexane followed by slow evaporation gave yellow crystals of 3‚CH2Cl2. Yield: 0.302 g, 85%. Anal. Calcd for C29H47NNiO2P2S2‚CH2Cl2: C, 50.65; H, 6.94; N, 1.97. Found: C, 50.33; H, 6.81; N, 1.83. IR (14) Barrado, G.; Hricko, M. M.; Miguel, D.; Riera, V.; Wally, H.; Garcı´a-Granda, S. Organometallics 1998, 17, 820.

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(CH2Cl2): ν(CN) 2151 cm-1. 1H NMR (CDCl3; δ (ppm)): 7.23 (t(7), 1H, H4 of Xyl), 7.12 (d(7), 2H, H3and H5of Xyl), 4.08 (m (br), 2H, POCH2), 2.42 (s, 6H, CH3 of Xyl), 2.07 to 1.25 (m, 33H, Cy), 1.33 (m, 3H, POCH2CH3). 31P{1H} NMR δ 56.9 (d(12), S2PO), 42.5 (d(12), PCy3). (b) From 2. To a solution of 2 (0.346 g, 0.5 mmol) in CH2Cl2 (15 mL) was added PCy3 (0.28 g, 1 mmol), and the mixture was stirred at room temperature for 30 h. The solvent was evaporated to dryness, and the residue was washed with Et2O (2 × 5 mL). The solid was recrystallized from CH2Cl2/hexane. Yield: 0.26 g, 73%. (c) From 4. To a solution of 4 (0.24 g, 0.5 mmol) (see below) in CH2Cl2 (15 mL) was added PCy3 (0.28 g, 1 mmol), and the mixture was stirred at room temperature for 24 h. The solvent was evaporated to dryness, and the residue was washed with Et2O (2 × 5 mL). The solid was recrystallized from CH2Cl2/ hexane. Yield: 0.293 g, 80%. [Ni{S2P(O)(OEt)}(CNXyl)2] (4). To a red solution of 2 (0.345 g, 0.5 mmol) in CH2Cl2 (20 mL) was added PCy3 (0.14 g, 0.5 mmol), and the mixture was stirred at room temperature for 10 h. The color changed slowly to red-brown. The solvent was evaporated in vacuo, the residue was washed with hexane and redissolved in CH2Cl2/hexane (1/1, v/v), and the solution was chromatographed on silica. Elution with CH2Cl2/hexane (1/1, v/v) gave a purple band consisting of a small amount of purple 1. Further elution with THF gave a red-orange band containing compound 4. Addition of hexane and slow evaporation gave 4 as orange crystals. Yield: 0.174 g, 73%. Anal. Calcd for C20H23N2NiO2PS2: C, 50.34; H, 4.86; N, 5.87. Found: C, 50.16; H, 5.03; N, 5.72. IR (CH2Cl2): ν(CN) 2192, 2175 cm-1. 1 H NMR (CDCl3; δ (ppm)): 7.28 (t(7), 2H, H4 of Xyl), 7.14 (d(7), 4H, H3and H5of Xyl), 4.12 (m, 2H, POCH2), 2.42 (s, 12H, CH3 of Xyl), 1.35 (m, 3H, POCH2CH3). 31P{1H} NMR (δ (ppm)): 54.4. [Ni{S2P(OEt)2}{2-pyCHdNC6H4-Me-4}2][S2P(OEt)2] (5). To a solution of 1 (0.214 g, 0.5 mmol)6 in CH2Cl2 (15 mL) was added 2-pyCHdNC6H4-Me-4 (0.196 g, 1 mmol). The mixture was stirred at room temperature for 2 h. The color of the solution changed from purple to red-brown. The solvent was evaporated to dryness, and the residue was washed with

Boı´llos and Miguel hexane (3 × 10 mL). The resulting solid was recrystallized from CH2Cl2/hexane to obtain orange crystals of 5. Yield: 0.275, 67%. Anal. Calcd for C34H44N4NiO4P2S4: C, 49.70; H, 5.40; N, 6.82. Found: C, 49.63; H, 5.18; N, 6.51. X-ray Diffraction Studies. Crystals were grown by slow diffusion of hexane into concentrated solutions of the complexes in CH2Cl2 at -20 °C. Relevant crystallographic details are given in Table 1. Intensity measurement was made with a Bruker AXS SMART 1000 diffractometer with graphitemonochromated Mo KR X-radiation and a CCD area detector. A hemisphere of the reciprocal space was collected up to 2θ ) 48.6°. Raw frame data were integrated with the SAINT15 program. The structures were solved with SHELXTL.16 A semiempirical absorption correction was applied with the program SADABS.17 All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were set in calculated positions and refined as riding atoms, with a common thermal parameter. All calculations and graphics were made with SHELXTL.

Acknowledgment. We thank the Spanish MCYT (Project BQU2002-03414) and Junta de Castilla y Leo´n (VA052/03) for financial suppot and the MEC (Program F.P.U.) for a grant to E.B. Supporting Information Available: Complete tables of atomic coordinates, anisotropic thermal parameters, and bond lengths and angles for the structures of 2-5; these data are also available as CIF files. This material is available free of charge via the Internet at http://pubs.acs.org. OM0343364 (15) SAINT+: SAX area detector integration program, Version 6.02; Bruker AXS, Inc., Madison, WI, 1999. (16) Sheldrick, G. M. SHELXTL, An Integrated System for Solving, Refining, and Displaying Crystal Structures from Diffraction Data, Version 5.1; Bruker AXS, Inc., Madison, WI, 1998. (17) Sheldrick, G. M. SADABS, Empirical Absorption Correction Program; University of Go¨ttingen, Go¨ttingen, Germany, 1997.